DE1720489A1 - Process for the production of polyesters from halogenated, dihydric phenols - Google Patents

Description

Demonstrations for the production of polyesters from halogenated, divalent ones Phenols (rB vsatz zur Pawtentanmeldung D 51 835 IVd / 39 c) Subject matter of the invention the patent application D 51 835 IVd / 39 c is a process for the production of Polvestern from halogenated, dihydric phenols and acid chlorides, second, ready-to-use carbic acid. The process is special, characterized in that the carboxylic acid chlorides are used with the halogenated, dihydric phenols in the presence of catalytic amounts tertiary amines whose amino groups are not part of an aromatic ring system is, e7nenenfa7, using solvents, at a temperature of 50 - 250 ° CV, at times 80 - 180 ° C.

If modification of this process for the production of polyesters according to # Patent application D 51 835 IVd / 39 c has now been found that the implementation also in the presence of catalytic amounts of tertiary amines, the amino group of which is Be component an aromatic ring system inst, and / @@@@@ possibly N-mono- or disub -stituierten Acid amides can perform.

Dicarboxylic acid chlorides are used to produce the polyester of the halogenated Dinherele ride and halore-valued diphenols are preferably used in a stoichiometric ratio, i.e., per mole of dicarboxylic acid chloride becomes 1 mole of halogenated dihydric phenol used. An excess of up to 5 mol% of the phenol can be used to produce the desired the - iei.

The use of an excess of dihydric phenols allows the production of oligoneren hzw. Polymers with hydroxyl end groups. The usage Substoichiometric amounts of dihydric phenols, on the other hand, lead to products with chlorine end groups.

The process can be carried out with uniform and mixed, tert. Amines, their amino group is also part of an aroma. table ring system can be, and / or possibly N-mono- or disubstituted acid amides or

Imides are carried out, substituted laide in the sense of present invention is to be regarded as a type of cyclic amide.

Suitable aromatic, tert. An-ine are quinoline, isoquinoline, pyrazine, Oxazine, oxazole, thiazole, oxdiazole, bezthiazole and the like.

Suitable, optionally N-mono- or disubstituted acid amides are the carboxamides of monobasic aliphatic, aromatic and araliphatic Carbene acids with 1 to 18 carbon atoms.

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@@@@@. @ enric acid, bergoic acid, phenylacetic acid and, .. Ty:, .. ~ ^ ~., -.: ,, - y.P '-; - y; fsy .-:' tnj> f, -1-'ir ^ nr "3 (? 1-, ~ rr.> t.; Pj, ry - (- like i @ the Beaztra @bemsäure, acetoacetic acid or ivulinic acid, be interrupted. as Bases that denote the in Betnacht .'o "(" .nrPistrabe'eure, ". Cetesl.r'reoderIvrT -''- Anmonick or mono- or diamines. Primary or secondary mono- or diamines are preferred, which differ from the saturated, aliphatic, araliphatic, cycloaliphatic Series or derive from the arematic series with only one @rometic ping. For example, methylamine, dimethylamine, di-n- or -i-propylamine, Di-n- or -sio-butylamine, di-2-methylhexylamine, dilaurylamine, ethylenediamine, tetramethylendiemir, Hexamethylenediamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, Aniline, N-methylamiline, toluidine, phenylenediamine and hexahydropohenylenediamine called. One or both alkyl groups of the amines can also be replaced by the phanyl or toluyl radical or by cycloalkyl groups with 5 to 6 ring carbon atoms, which optionally or substituted by alkyl groups, in particular one or two methyl groups can be replaced or substituted. Tone the nln s amino component for the Particularly suitable diamines are used to prepare the amides mentioned, in donated the two amino groups by one to g methylene groups are separated. In the diamonds, too, those still bound to the nitrogen atom can be found Hydrogen atoms except for at least one, e.g. B. by alkyl groups with 1 to 4 carbon atoms, the phenyl or toluyl radical or r a 5- to 6-membered cycloalkyl radical be. As representatives of particularly suitable carboxamides, which are used as catalysts are used according to the invention # can be listed by name: formamide, Methylformamide, acetamide, N, N-dimethylacetamide, N, N-di-n-or-i-nropylbutyrnwid, N, N-di-n-or-isobutylbutyramide, id, N-benzylbutyric acid amide, N, N-dipropyl-2-ethylhexanoic acid amide, Acetoacetic acid-N, N-di-n-butylamide, acetoacetic acid anilide, benzoic acid benzylamide, N, N-dimethylbenzoic acid anide, and N, N'-diformylhexamethylenediamine. Furthermore you can cyclic suramides or imides can also be used. vs barbitureheads also come as Eatalysatoren in Frae, which by Eohlenwasserstofreste, in particular by C.-C.-alkyl or phenyl groups can be substituted, such as dimethylbarbituric acid, Diethyl barbituric acid, di-propyl barbituric acid, diallyl barbituric acid, di-n-butyl barbituric acid and phenylethylbarbituric acid.

But also carbonic acid amides or carbonic acid imides, preferably the N-substituted ones Dert-rnte, such as N-phenyl urethane, diphenylcarbodiimide, diphenylguanidine can be used will. l'i.r'iidesinebenfallseeeK.ntalr'atore.like si-nrl-Tr Pyeidy] -sulfanilamide. Phosphorous acid amides, such as Au il, Tut ', N', N ", N" -hexamethylphosphorous acid triamide, N, N, N ', N', N ", N" -hexarethylphosphoric acid triamide, N, N, N ', N', N ", N" -hexa-n- or iso-butylphosphorus Acid trinamide and phosphorous acid trimorpholide can be used as catalysts will. The phosphoric acid triamides, which are also used as catalysts can, however, are somewhat inferior to phosphoric acid in their catalytic effect. mitansäureamide and tin n acid amides, such as di-n-propoxy -titanium diamide and di-r- or -iso-butyltin diamide, can be s

It is not necessary for the catalysts to already be finished Amides to apply directly. Rather, one can also find the coronents from which never build up, 3. B. a n mixture of a primary or secondary mono- or Diamine of the type mentioned above and one of the mentioned nonooarboxylic acids or use the acid chlerides or anhydrides derived from these acids, because the acid amides then form under the reaction conditions.

Of course, mixtures of the aforementioned amines and -il-s can be used as Catalysts are used. Gemieche mSt-tert. ATnines of the main application D 51 835 IVd / 3 ° c hzw. their auaternary ammonium salts, such as tri-methylbenzylammonium chloride, Triethylbenzylammonium hydroxide or acetate or triethylammonium hydrochloride can be used.

Pyridine, which in itself has a very good catalytic effect, At higher temperatures of conversion, it sublimes in the form of the resulting pyridine hydrochloride. As a result, the catalytic converter leaves its catalytic effect during the conversion after. It is therefore advisable to use pyridine in combination with other knees or to be used as a catalyst or: but to apply pressure in the reaction.

The tertiary amines and acid amides used as catalysts are in amounts of 0.1-20 mol%, preferably 0.2-2 mol, based on the acid halide, used.

, e can do the approaches at once as well as in several small ones Portions are added.

The condensation occurs under the conditions according to the invention. sch with the release of practically stoichiometric amounts of gaseous HCl. The enclosed FIGS. 1 and 2 clearly have this advantage. Figure 1 illustrates the time course of the HCl elimination rate of An: dtzen from 36.6 g of tetrachlorobisphenol A, 16.7 g sebicic acid dichloride and 6.09 terenhthalic acid dichloride 100 ml boiling o-dichlorobenzene.

This means: 1. without Katnlysetor 2. in the presence of 1, related on the amount of acid chloride, di-p-tolylcarbodiimide, 3. "" "" "N, N, N ', N', N", N "-hexanemethylphosphoric acid triamide, * in 4. in Gogenwart of 1% by weight based on the amount of acid chloride, N, N-dimethylcyclohexylamine, 5. "" "" ", tetramethylammonium chloride 6." "" " ", Quinoline and 7." "" "", formamide figure shows the same determination for Batches made from 36.6 g of Tetrnbisphenol A, 12.2 g of terephthalic acid dichloride and 8.1 g Isophthalic acid dichloride in 100 ml of boiling o-dichlorobenzene.

It means in FIG. 2: without catalyst a in the presence of 1 wt. obsessed on the amount of acid chloride, N, N, N ', N', N ", N" -hexamethylphosphorous acid trianide 10. "" "" ", di-p-tolylcarbodiimide 11." "" "", fornamide 12. "" "" ", tetramethylammonium chloride and 13. quinoline.

The reaction can take place either in the melt or in inert solvents be carried out, the inert solvent both the function of a real Solvent can possess as well as that of a dispersant. Suitable solution means within the meaning of the present invention are already mentioned in the main application. Solvents such as chlorj are also suitable. erte aliphatic and aromatic Hydrocarbons, e.g.

Tetrachloroethane, tetrachlorethylene, pentachloroethane, trichlorobenzene, Dichloroethyl benzene, etc., alkylbenzenes, such as isomer mixtures of hexylcumene, cyclohexyltcluene, Cyclohexylethylbenzene. Isopropylethylbenzene. Dihexcylbenzene, di-p-tolylmethane, nitrobenzene and phenyl ethers and diphenyl.

Otherwise the convertible starting products correspond to sum purchführung of the method according to the invention and the conditions for setting up those of the main message.

The end products can be worked up by methods known per se take place. If solvents are used as the condensation medium, the insulation the polyester by pulling the solvent or by precipitation, ideally with polar solvents such as methanol, ethanol, acetone, tetrahydrofuran etc., of the polymer can be obtained.

The polymers can be used in a manner known per se after removing the Solvent can be condensed in the melt under vacuum. at the most expedient at a vacuum of 0.01 to 4 mm Hg and a temperature 20 ° C above the Schrelz range pn Poplymeren. The polymers produced can be made to Foli rarh known method be processed. They can also be used as cast films made from solutions of chlorinated hydrocarbons getting produced.

Illustrate various embodiments of the method according to the invention the following examples: Example 1: In a three-necked flask, provided with Stirrer, condenser and inlet pipe, were 73, 2 (0,? Mol) 2, 2-Bi s- (3,5-dichloro-4-hydroxyphenyl) -propane, 24.36 g (0.12 mol) terephthalic acid dichloride, 16.24 g (0.08 mol) isophthalic acid dichloride, 0.3 ml of pyridine and 0.2 ml of IT, N-dimethylcyclohexylamine in 250 ml of o-dichlorobenzene brought to reaction. The reaction mixture was boiling below T nuf the o-dichlorobenzene contents.

After 8 hours, the theoretical amount of hydrogen chloride had been split off. The product was extracted with methanol and dried.

The product has a melting range of 300 - 350 ° C and a red. Viscosity (determined in chloroform as a 0.5% strength by weight solution at 25 ° C.) of 0.56 (yield :%.

Example 2: In a three-necked flask equipped with a stirrer, Kilhler and FinTeitungsrohr, were 73.2 g (0.2 mol) 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 28.42 grams (0.14 moles) of derephthalic acid dichloride; 12.18 g (0.06 mol) isophthalic acid dichloride, 0.3 ml of pyridine and 0.2 ml of N-dimethsr1-cyclchexylamine in 250 ml of dichlorobenzene brought about the reaction. The reaction mixture was stirred at the boiling point of o-dichlorobenzene held.

After about 23 hours, the theoretical amount of hydrogen chloride had been split off. The product was precipitated with methanol and dried. The product has one Melting range from 300 - 340 ° C and a red. Viscosity of 0.5%, determined as in Example 1, from 0.65. Yield: approx. 98% Example 3: In a three-necked flask, equipped with stirrer, Kibler and Finleitungsrohr, we were 36.6 g?, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) -pyropane, 10.15 g of terephthalic acid dichloride, 10.15 g of isophthalic acid dichloride with 0.15 ml of quinoline reacted in 120 ml of o-dichlorobenzene. The reaction mixture was under Stirring kept at the boiling point of the o-dichlorobenzene until the theoretical Amount of hydrogen chloride was split off.

The product was precipitated with methanol and dried.

The polygster has a melting range of 300-330 ° C and a red. Viscosity (determined as in Example 1) of 0. 64. Yield: approx.%.

Example 4: In a three-necked flask, given away with stirrer, cooler and pin conduit pipe, 36.6 g of 2,2-bis (3,5-dichloro-4-hydroxyphenyel) propane, 11.96 g sebacic acid dichloride, 10.15 g terephthalic acid dichloride, 0,? nl tri-n-butylamine and 0.3 g p! or'h -! -! ndn1? 0mlo-Dchlobenzolrruretio @ehracht. The reaction mixture was kept with stirring at the boiling point of o-dichlorobenzene until the Theoretical amount of hydrogen chloride had been split off. The d precipitated with methanol. The polyester has a melting range of 260-310 ° C and a red. Viscosity 0.5% (beys. ur as described in Example 1) of 0.88.

Yield: approx. 98%.

Example 5: Using Example 1, 38.3 g of?, 2-bis- (3, 5-dibron-4-hydroxyphenyl) propane, 47.6 g?, 2-bis (3,5-dichloro-4-? Hydroxyphenyl) propane, 20.3 terephthalic acid dichloride, 20.3 g of isophthalic acid dichloride in 250 ml of o-dichlorobenzene in the presence of 0.5 ml Quinoline reacted.

N.r'BepndJmderfilsurebspaltun was the product precipitated with methanol and dried at 170 ° G in the tartar. The polyester has a melting range of 300 - 345 ° C, red. Viscosity (in a phenol-tetrachloroethane mixture 60:40 parts by weight determined as a 0.5 Ge% solution at 25 ° C) 0.62.

Example 6: Analogously to Example 1, 36.6 g of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane were used and 16.7 g of sebacic acid dichloride with 0.5 ml of di-n-butylbenzoic acid amide as a catalyst brought to reaction in 1 ° 0 ml of o-dichlorobenzene. After 60% of the theoretical Amount of HCZ was split off, anuries 6.09 g of terephthalic acid dichloride were added. To Upon completion of the hydrochloric acid cleavage, the polymer was precipitated with methanol and dried at 170 ° C under Valmum, melting range 245-280 ° C, red. Viscosity (determined as described in Example 1) 0.66.

Claims (3)

P a t e n t a n s p r ü c h e: 1. Change of the procedure for Production of polyesters from halogenated, dihydric phenols tlY7, acid chlorides divalent carboxylic acids according to patent application 051 835 IV d / 39 c, whereby the onsaurechloride carbonic acid chlorides with the halogenated, dihydric phenols in the presence of catalytic amounts of tertiary amines, the amino group of which is not included an aromatic ping system, if necessary using inert solvents, at a temperature of 50-250 ° C, preferably n-190 ° C, thereby marked that there are empty tertiary groups whose amino groups are not part of a aromatic ring system is tertiary amines, the amino group of which is part of a aromatic ring systems, and / or optionally. N-mono- or disubstituted acid amides used. 2. The method according to claim 1, characterized in that nan the tertiary amines bw. Acid amides are used in the form of their quaternary ammonium compounds. 3. The method according to claim 1, characterized in that there. ß man ala Saureamid Carbodi jmide uses.